The class of polymers of carbon monoxide and olefin(s) is well known in the art. Brubaker, U.S. Pat. No. 2,495,286, produced such polymers of relatively low carbon monoxide content in the presence of free radical initiators, e.g., peroxy compounds. G.B. 1,081,304 produced similar polymers of higher carbon monoxide content in the presence of an aklylphosphine complex of palladium salts as catalyst. Nozaki extended the reaction to produce linear alternating polymers in the presence of arylphosphine complexes of palladium moieties and certain inert solvents. See, for example, U.S. Pat. No. 3,694,412.
More recently the class of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon has become of greater interest in part because of the greater availability of the polymers. The more recent general processes for the production of these linear alternating polymers, now becoming known as polyketones or polyketone polymers, are illustrated by a number of published European patent applications including 121,965, 181,014, 213,671, and 257,663. These processes typically involve the use of a catalyst composition produced from a compound of certain Group VIII metals, particularly a palladium compound, the anion of a strong non-hydrohalogenic acid and a bidentate ligand of phosphorus, arsenic or antimony, particularly phosphorus. The addition of excess monophosphine to such catalyst compositions has been disclosed but the addition generally has had an adverse effect. In published European patent application 121,965 the activity of a polymerization catalyst decreased when 30 mols of monophosphine were added per mol of palladium. In published European Patent Application 283,092 it is shown that polymerization to form a linear alternating polymer stops when as little as 8 mols of a monophosphine per mol of palladium is provided. It would be of advantage to provide a process for the production of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon wherein the addition of certain monophosphines or phosphine oxides produces an increase in the activity of the polymerization catalyst composition.